The present invention relates to the use of metal complexes of tripodal ligands based on tris(2-aminoethyl)amine as catalysts which enhance the action of peroxygen compounds in washing, cleaning and disinfecting processes. The invention further relates to compositions of the metal complexes and peroxygen compounds used in such processes and to the novel metal complexes and ligands and also to processes for preparing them.
It is known that some manganese complexes, especially those of the salene type, are useful catalysts for oxidations with peroxygen compounds, especially as part of a washing processes. It is also known that certain other manganese complexes have a marked bleaching effect on dirt and dyes in wash liquors. There is nevertheless a demand for further compounds having an improved effect and/or having a broader application range, subject to the proviso that no significant fibre and dye damage may occur when applied to textile material.
It has now been found that certain metal complexes of tripodal ligands obtainable by reacting tris(2-aminoethyl)amine with aldehydes or ketones substantially meet the stated requirements when used as catalysts in that they enhance the action of peroxygen compounds in a wide variety of applications to a higher degree without occurrence of fibre and dye damage. Surprisingly, the enhanced effect occurs in applications including the following on using the metal complexes of such ligands in aqueous solution together with peroxygen compounds:
a) bleaching spots or stains on textile material as part of a washing process,
b) preventing the redepositon of migrating dyes during the washing of textile material,
c) cleaning hard surfaces, especially crockery or glass,
d) cleaning hard surfaces, especially tiles, particularly to remove mold stains,
e) using washing and cleaning solutions having an antibacterial effect, and
f) removing printing inks from printed wastepaper (de-inking).
The invention accordingly provides for the use of metal complexes containing a tripodal ligand of the formula 
where
R1, R2, R3, R4, R1xe2x80x2, R2xe2x80x2, R3xe2x80x2, R4xe2x80x2, R1xe2x80x3, R2xe2x80x3, R3xe2x80x3 and R4xe2x80x3 are each independently hydrogen, cyano, halogen, SO3M, where M is hydrogen, an alkali metal cation, an alkaline earth metal cation, ammonium or an organic ammonium cation, SO2NH2, SO2NHR5, SO2N(R5)2, OR5 or COOR5, where R5 is hydrogen or linear or branched C1-C4alkyl, nitro, linear or branched C1-C8alkyl, linear or branched fluorinated or perfluorinated C1-C8alkyl, NHR6, R6NR7, N⊕R6R7R10 or linear or branched C1-C8alkyl-R8, where R8 is OR5, COOR5, NH2, NHR6, NR6R7 or N⊕R6R7R10, where R6, R7 and R10 are identical or different and each is linear or branched C1-C12alkyl or where R6 and R7 combine with the joining nitrogen atom to form a 5-, 6- or 7-membered ring, which may contain further heteroatoms, and where R9, R9xe2x80x2 and R9xe2x80x3 are each independently hydrogen, linear or branched C1-C8alkyl or aryl, as catalysts for oxidations with peroxygen compounds.
Particular preference is given to the use of Mn(III) and Fe(III) complexes containing a ligand of the above formula (1), especially an Mn(III) and Fe(III) complex which contains a ligand of the above formula (1) and metal in a molar ratio of 1:1.
Halogen is preferably chlorine, bromine or fluorine, particularly preferably chlorine.
Alkyl is particularly alkyl having 1 to 4 carbon atoms, especially methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R6 and R7 combining with the joining nitrogen atom to form a 5-, 6- or 7-ring are in particular a pyrrolidine, piperidine, morpholine or piperazine ring. The piperazine ring may be substituted, for example by alkyl, on the nitrogen atom not attached to the phenyl or alkyl radical.
Aryl is for example naphthyl or particularly phenyl.
R9, R9xe2x80x2 and R9xe2x80x3 are each preferably independently hydrogen or C1-C4alkyl, especially hydrogen.
An alkali cation M in the SO3M radicals may be for example lithium, potassium or particularly sodium, an alkaline earth metal cation M is selected in particular from magnesium and calcium.
Very particular preference is given to the use of the 1:1 Me(III) complexes of the formula 
where Me is Mn or Fe, R1, R1xe2x80x2 and R1xe2x80x2 are each independently hydrogen, C1-C4alkyl, C1-C4alkoxy, hydroxyl, nitro, NHR6, NR6R7 or -N⊕R5R6R7, where R5, R6 and R7 are each independently C1-C4alkyl, as catalysts for oxidations with peroxygen compounds.
Me in the formula (2) is preferably manganese.
The metal complexes containing a tripodal ligand of the formula (1) are preferably used in aqueous solution together with peroxygen compounds for bleaching spots or stains on textile material or for preventing the redeposition of migrating dyes as part of a washing process, or for cleaning hard surfaces, especially crockery or glass.
The ligands of the formula (1) are also useful in the uncomplexed form, as catalysts in aqueous solution with peroxygen compounds for bleaching spots or stains on textile material.
Preference for this use is given to the ligands of the formula 
where
R1, R1xe2x80x2 and R1xe2x80x3 are each independently hydrogen, C1-C4alkyl, C1-C4alkoxy, hydroxyl, nitro, NHR6, NR6R7 or N⊕R5R6R7, where R5, R6 and R7 are each independently C1-C4alkyl and R2, R2xe2x80x2 and R2xe2x80x3 are each independently hydrogen, linear or branched C1-C8alkyl or aryl.
Individual metal complexes containing a tripodal ligand of the formula (1) are already known, for example from S. Chandra, P. Chakraborty, A. Charkaravorty, J. Chem. Soc., Dalton Trans. (1993), 6,863. Novel metal complexes are the manganese(III) and iron(III) complexes containing a tripodal ligand of the formula 
where R1, R2, R3, R4, R1xe2x80x2, R2xe2x80x2, R3xe2x80x2, R4xe2x80x2, R1xe2x80x3, R2xe2x80x3, R3xe2x80x3 and R4xe2x80x3 are each independently hydrogen, cyano, halogen, SO3M, where M is hydrogen, sodium, calcium, magnesium, ammonium or an organic ammonium cation, SO2NH2, SO2NHR5, SO2N(R5)2., OR5 or COOR5, where R5 is hydrogen or linear or branched C1-C4alkyl, nitro, linear or branched C1-C8alkyl, linear or branched fluorinated or perfluorinated C1-C8alkyl, NHR6, NR6R7, NR⊕R6R7R10 or linear or branched C1-C8alkyl-R8, where R8 is OR5, COOR5, NH2, NHR6, NR6R7 or N⊕R6R7R10, where R6, R7 and R10 are identical or different and each is linear or branched C1-C12alkyl or where R6 and R7 combine with the joining nitrogen atom to form a 5-, 6- or 7-membered ring, which may contain further heteroatoms, and where R9, R9xe2x80x2 and R9xe2x80x3 are each independently hydrogen, linear or branched C1-C8alkyl or aryl, subject to the condition that in the manganese(III) complex at least one of the substituents R1, R2, R3, R4, R1xe2x80x2, R2xe2x80x2, R3xe2x80x2, R4xe2x80x2, R1xe2x80x3, R2xe2x80x3, R3xe2x80x3, R4xe2x80x3, R9, R9xe2x80x2 and R9xe2x80x3 has a meaning other than hydrogen and that at least one of the substituents R3, R3xe2x80x2 and R3xe2x80x3 has a meaning other than chlorine when the substituents R1, R2, R4, R1xe2x80x2, R2xe2x80x2, R4xe2x80x2, R1xe2x80x3, R2xe2x80x3, R4xe2x80x3, R9, R9xe2x80x2 and R9xe2x80x3 are all hydrogen.
These manganese(III) and iron(III) complexes also form part of the subject-matter of the present invention. They are obtained in a conventional manner by reacting a ligand of the formula (1) with a manganese or iron compound to form the corresponding metal complex. Such methods of operation are described for example in U.S. Pat. No. 5,281,578 and No. 4,066,459. Also new are the ligands of the formula 
where
R1, R2, R3, R4, R1xe2x80x2, R2xe2x80x2, R3xe2x80x2, R4xe2x80x2, R1xe2x80x3, R2xe2x80x3, R3xe2x80x3 and R4xe2x80x3 are each independently hydrogen, cyano, halogen, SO3M, where M is hydrogen, an alkali metal cation, an alkaline earth metal cation, ammonium or an organic ammonium cation, SO2NH2, SO2NHR5, SO2N(R5)2., OR5 or COOR5, where R5 is hydrogen or linear or branched C1-C4alkyl, nitro, linear or branched C1-C8alkyl, linear or branched fluorinated or perfluorinated C1-C8alkyl, NHR6, NR6R7, N⊕R6R7R10 or linear or branched C1-C8alkyl-R8, where R8 is OR5, COOR5, NH2, NHR6, NR6R7 or N⊕R6R7R10, where R6, R7 and R10 are identical or different and each is linear or branched C1-C12alkyl or where R6 and R7 combine with the joining nitrogen atom to form a 5-, 6- or 7-membered ring, which may contain further heteroatoms, and where R9, R9xe2x80x2 and R9xe2x80x3 are each independently hydrogen, linear or branched C1-C8alkyl or aryl, subject to the condition that at least one of the substituents R1, R2, R3, R4, R1xe2x80x2, R2xe2x80x2, R3xe2x80x2, R4xe2x80x2, R1xe2x80x3, R2xe2x80x3, R3xe2x80x3, R4xe2x80x3, R9, R9xe2x80x2 and R9xe2x80x3 has a meaning other than hydrogen and that at least one of the substituents R3, R3xe2x80x2 and R3xe2x80x3 has a meaning other than chlorine when the substituents R1, R2, R4, R1xe2x80x2, R2xe2x80x2, R4xe2x80x2, R1xe2x80x3, R2xe2x80x3, R4xe2x80x3, R9, R9xe2x80x2 and R9xe2x80x3 are all hydrogen.
These ligands likewise form part of the subject-matter of the present invention. They are obtained in a conventional manner, for example by reacting tris(2-aminoethyl)amine with 3 mol of the substituted or unsubstituted salicylaldehyde. Reacting stepwise with three different salicylaldehydes or with mixtures of two or three different salicylaldehydes provides ligands of the formula (1) where the three aromatic rings have different substituents.
The metal complexes containing a tripodal ligand of formula (1) may before their use be converted into a solid or liquid preparation comprising the metal complex containing a tripodal ligand of the formula (1), a dispersant and optionally further ingredients and water.
It is advisable to grind the metal complexes, preferably to an average particle size of less than 20 xcexcm, especially between 0.1 and 15 xcexcm. Grinding may be effected together with the dispersants and further ingredients in dry form, but wet grinding is preferred. Grinding is effected in a conventional manner and in customary mills. The dry preparations obtained may be used in this form or may be slurried up in a solvent or water and used in the form of a suspension. Suspensions obtained from wet grinding may be used as such or may be dried and used in the form of solid preparations.
The present invention accordingly further provides aqueous suspensions comprising
a) 1-60% by weight, preferably 5-30% by weight, of a metal complex containing a tripodal ligand of the formula (1),
b) 0.5 to 15% by weight, preferably 1-5% by weight, of a dispersant,
c) 0-10% by weight of a further ingredient, and
d) 15-98.5% by weight of water.
The present invention further provides solid preparations comprising
a) 1-99% by weight, preferably 5-50% by weight, of a metal complex containing a tripodal ligand of the formula (1),
b) 1 to 99% by weight, preferably 50-95% by weight, of a carrier material,
c) 0-20% by weight of a dispersant,
d) 0-10% by weight of a further ingredient, and
e) 0-5% by weight of water.
Useful dispersants include in particular anionic dispersants and nonionic dispersants.
The anionic dispersants used include for example commercially available water-soluble anionic dispersants for dyes, pigments. etc. Useful products include in particular condensation products of aromatic sulfonic acid and formaldehyde, condensation products of aromatic sulfonic acids with possibly chlorinated biphenyls or diphenyl oxides and optionally formaldehyde, (mono/di-)alkylnaphthalenesulfonates, sodium salts of polymerized organic sulfonic adds, sodium salts of polymerized alkylnaphthalenesulfonic acid, sodium salts of polymerized alkylbenzenesulfonic acid, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acid, sodium salts of alkyldiglycol ether sulfates, sodium salts of polynaphthalenemethanesulfonates, lignin- or oxyligninsulfonates or heterocyclic polysulfonic acids.
Particularly useful anionic dispersants are condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerized organic sulfonic acids, (mono/di-)alkylnaphthalenesulfonates, polyalkylated polynuclear arylsulfonates, sodium salts of polymerized alkylbenzenesulfonic acid, ligninsulfonates, oxyligninsulfonates and condensation products of napthalenesulfonic acid with the polychloromethylbiphenyl.
Useful nonionic dispersants include in particular water-emulsifiable, -dispersible or -soluble compounds having a melting point of at least 35xc2x0 C. The following compounds are concerned, for example:
1. fatty alcohols having 8 to 22 carbon atoms, especially cetyl alcohol,
2. addition products of preferably 2 to 80 mol of alkylene oxide, especially ethylene oxide, in which case individual ethylene oxide units may be replaced by substituted epoxides, such as styrene oxide and/or propylene oxide, with higher saturated or unsaturated monoalcohols, fatty acids, fatty amines or fatty amides of 8 to 22 carbon atoms or with benzyl alcohols, phenylphenols, benzylphenols or alkylphenols whose alkyl radicals have at least 4 carbon atoms,
3. alkylene oxide, especially propylene oxide condensation products (block polymers),
4. ethylene oxide-propylene oxide adducts with diamines, especially ethylenediamine,
5. reaction products of fatty acid of 8 to 22 carbon atoms and a primary or secondary amine having at least one hydroxyloweralkyl or loweralkylloweralkyl group, or alkylene oxide addition products of these hydroxyalkyl-containing reaction products,
6. sorbitan esters, preferably having longchain ester groups, or ethoxylated sorbitan esters, for example polyoxyethylene sorbitan monolaurate having 4 to 10 ethylene oxide units or polyoxyethylene sorbitan trioleate having 4 to 20 ethylene oxide units,
7. addition products of propylene oxide with a tri- to hexahydric aliphatic alcohol of 3 to 6 carbon atoms, for example glycerol or pentaerythritol, and
8. fatty alcohol polyglycol mixed ethers, especially addition products of 3 to 30 mol of ethylene oxide and 3 to 30 mol of propylene oxide with aliphatic monoalcohols of 8 to 22 carbon atoms.
Particularly useful nonionic dispersants are surfactants of the formula
R11xe2x80x94Oxe2x80x94(Alkylenxe2x80x94O)nxe2x80x94R12xe2x80x83xe2x80x83(4)
where
R11 is C8-C22alkyl or C8-C18alkenyl;
R12 is hydrogen, C1-C4alkyl; a cycloaliphatic radical having at least 6 carbon atoms or benzyl;
xe2x80x9cAlkylenxe2x80x9d is an alkylene radical of 2 to 4 carbon atoms, and
n is from 1 to 60.
The substituents R11 and R12 in the formula (4) are advantageously the hydrocarbon radical of an unsaturated or preferably saturated aliphatic monoalcohol of 8 to 22 carbon atoms. The hydrocarbon radical may be straight-chain or branched. Preferably R11 and R12 are each independently an alkyl radical of 9 to 14 carbon atoms.
Useful aliphatic saturated monoalcohols include natural alcohols, for example lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and also synthetic alcohols, for example 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethyinonyl alcohol, decanol, C9-C11 oxo alcohol, tridecyl alcohol, isotridecyl alcohol or linear primary alcohols (Alfols(trademark)) having 8 to 22 carbon atoms. Some representatives of these Alfols are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18).
Examples of unsaturated aliphatic monoalcohols are dodecenyl alcohol, hexadecenyl alcohol and oleyl alcohol.
The alcohol radicals may be present individually or in the form of mixtures of two or more components, for example as mixtures of alkyl and/or alkenyl groups derived from soybean fatty acids, palm kernel fatty acids or tallow oils.
(Alkylen-O) chains are preferably divalent radicals of the formulae 
Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyl or preferably cyclohexyl.
Preferred nonionic dispersants are surfactants of the formula 
where
R13 is C8-C22alkyl;
R14 is hydrogen or C1-C4alkyl;
Y1, Y2, Y3 and Y4, are independently hydrogen, methyl or ethyl;
n2 is from 0 to 8; and
n3 is from 2 to 40.
Further important nonionic dispersants conform to the formula 
where
R15 is C9-C14alkyl;
R16 is C1-C4alkyl;
Y5, Y6, Y7 and Y8, are independently hydrogen, methyl or ethyl, subject to the proviso that
one of Y5, Y6 on the one hand or Y7 and Y8 on the other is always hydrogen; and
n4 and n5, are independently an integer from 4 to 8.
The nonionic dispersants of the formulae (4) to (6) may be used as mixtures. Useful surfactant mixtures accordingly include for example non-end-group-capped fatty alcohol ethoxylates of the formula (4), ie. compounds of the formula (4) where
R11 is C8-C22alkyl.
R12 is hydrogen and
the Alkylen-O chain is the radical xe2x80x94(CH2xe2x80x94CH2xe2x80x94O)xe2x80x94,
and also end-group-capped fatty alcohol ethoxylates of the formula (6).
Examples of the nonionic dispersants of the formulae (4), (5) or (6) are reaction products of a C10-C13 fatty alcohol, for example of a C13 oxo alcohol, with 3 to 10 mol of ethylene oxide, propylene oxide and/or butylene oxide, or the reaction product of one mole of a C13 fatty alcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide. The addition products may each be end-group-capped by C1-C4alkyl, preferably methyl or butyl.
These dispersants may be used individually or as mixtures of two or more dispersants.
Useful carrier materials Include for example: solid Inorganic compounds possessing little if any hygroscopicity that are compatible with laundry detergent ingredients and are soluble or readily suspendible in water. Examples are oxides, such as MgO, CaO, TiO2, ZnO, Al2O3 and SiO2, especially Al2O3 and SiO2; borates, aluminates, silicates, carbonates, phosphates, sulfates and aluminosilicates (zeolites) of alkai and alkaline earth metals, especially of sodium and of potassium. The oxo anions in these compounds may be linked via oxygen atoms to form larger chains, rings, layers or three-dimensional networks.
Examples of further ingredients include wetting agents, water-insoluble or water-soluble dyes or pigments and also fillers and optical brighteners. These ingredients are present in an amount of 0 to 10% by weight based on the total weight of the solid or liquid preparation.
The metal complexes containing a tripodal ligand of the formula (1) are used as catalysts for oxidations with peroxygen compounds, for example for bleaching textile material, without causing significant damage to fibres and dyeings.
The present invention accordingly further provides a washing or cleaning process, which comprises adding to the liquor, which contains a peroxidic detergent, 0.1 to 200 xcexcmol per liter of wash liquor of one or more metal complexes containing a tripodal ligand of the formula (1).
The present invention further provides a process for preventing the redeposition of migrating dyes in a wash liquor, which comprises adding to the wash liquor, which contains a peroxidic detergent, 0.5 to 150, preferably 1.5 to 75, especially 7.5 to 40, mg per liter of wash liquor of one or more metal complexes containing a tripodal ligand of the formula (1).
The present invention also provides a laundry detergent comprising
I) 5-90%, preferably 5-70%, of A) an anionic surfactant and/or B) a nonionic surfactant,
II) 5-70%, preferably 5-50%, especially 5-40%, of C) a builder,
III) 0.1-30%, preferably 1-12%, of D) a peroxide, and
IV) 0.005-2%, preferably 0.02-1%, especially 0.1-0.5% of E) a metal complex containing a tripodal ligand of the above-defined formula (1), the percentages all being percent by weight based on the total weight of the laundry detergent
The laundry detergent may be in solid or liquid form, for example in the form of a liquid nonaqueous composition including not more than 5%, preferably from 0 to 1%, by weight of water, and be based on a suspension of a builder in a nonionic surfactant, as described for example in GB-A-2,158,454.
Preferably, however, the laundry detergent is powdered or granular.
A powdered laundry detergent may be produced for example by first producing a starting powder by spray drying an aqueous slurry containing all above-recited components except components D) and E) and then adding the dry components D) and E) and mixing everything together.
It is also possible to add component E) to an aqueous slurry containing components A), B) and C), then to spray dry and subsequently to mix component D) with the dry material.
It is also possible to start with an aqueous slurry which contains component A) and C), but component B) either not at all or only in part. The slurry is spray dried, then component E) is mixed with component B) and added, and subsequently component D) is mixed in dry.
The anionic surfactant A) can be for example a sulfate, sulfonate or carboxylate surfactant or a mixture thereof.
Preferred sulfates are sulfates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulfates whose alkyl radical possesses 10-20 carbon atoms.
Examples of preferred sulfonates are alkylbenzenesulfonates having 9-15 carbon atoms in the alkyl radical.
The cation in the anionic surfactants is preferably an alkali metal cation, especially sodium.
Preferred carboxylates are alkali metal sarcosinates of the formula Rxe2x80x94COxe2x80x94N(R1)xe2x80x94CH2COOM1, where R is alkyl or alkenyl having 8-18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl and M1 is an alkali metal.
The nonionic surfactant B) can be for example a condensation product of 3-8 mol of ethylene oxide with 1 mol of primary alcohol having 9-15 carbon atoms.
Builder C) may be for example alkali metal phosphate, especially tripolyphosphate, carbonate or bicarbonate, especially the sodium salt thereof, silicate, aluminosilicate, polycarboxylate, polycarboxylic acid, organic phosphonate, aminoalkylene-poly(alkylenephosphonate) or a mixture thereof.
Particularly useful silicates are sodium salts of crystalline sheet-silicates of the formula NaHSitO2t+1.pH2O or Na2SitO2t+1.pH2O, where t is between 1.9 and 4 and p is between 0 and 20.
Preferred aluminosilicates are those commercially available under the name zeolite A, B, X and HS and also mixtures comprising two or more of these components.
Preferred polycarboxylates are polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with maleic anhydride.
Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and also ethylenediaminedisuccinate not only in racemic form but also as the enantiomerically pure S,S-form.
Particularly useful phosphonates or aminoalkylenepoly(alkylenephosphonate)s are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta-methylenephosphonic acid. Peroxide component D) may be selected for example from the literature-described and commercially available organic and inorganic peroxides which bleach textile materials at customary washing temperatures, for example at 10 to 95xc2x0 C.
The organic peroxides concerned are for example mono- or polyperoxides, especially organic peracids or salts thereof, such as phthallmidoporexycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.
Preferably, however, inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates. It will be appreciated that mixtures of organic and/or inorganic peroxides may be used as well. The peroxides may be present in different crystal forms and with different water contents and they may also be used together with other organic or inorganic compounds to improve their stability in storage.
The peroxides are preferably incorporated into the laundry detergent by mixing of the components, for example by means of a screw metering system and/or a moving bed mixer.
In addition to the combination of the invention, the laundry detergents may include one or more optical brighteners, for example from the group consisting of bistriazinylamino-stilbenedisulfonic acid, bistriazolylstilbenedisulfonic acid, bisstyrylbiphenyl, bisbenzofuranyl-biphenyl, a bisbenzoxalyl derivative, a bisbenzimidazolyl derivative, a coumarin derivative and a pyrazoline derivative.
The laundry detergent may further include soil suspenders, for example sodium carboxymethylcellulose, pH regulators, for example alkali or alkaline earth metal silicates, foam regulators, for example soap, salts for controlling the spray drying and the granulating properties, for example sodium sulfate, scents and also optionally antistats, fabric conditioners, enzymes, such as amylase, bleaching agents, pigments and/or shading agents. It will be appreciated that these ingredients have to be stable with regard to the bleaching agent used.
Further preferred ingredients of the laundry detergents according to the invention are polymers to inhibit textiles that are being washed from being tainted by dyes in the wash liquor that have become detached from the textiles under the conditions of the wash. These polymers are preferably polyvinylpyrrolidones or polyvinylpyridine N-oxides, optionally modified through incorporation of anionic or cationic substituents, especially such polymers having a molecular weight in the range from 5000 to 60,000, especially from 10,000 to 50,000. These polymers are preferably used In an amount of 0.05 to 5% by weight, especially 0.2 to 1.7% by weight, based on the total weight of the laundry detergent.
The laundry detergents of the invention may additionally include perborate activators, for example TAED, TAGU or SNOBS. Preference is given to TAED, which is preferably used in an amount of 0.05 to 5% by weight, especially 0.2 to 1.7% by weight, based on the total weight of the laundry detergent.
Surprisingly, metal complexes containing a tripodal ligand of the formula (1) also have a significantly improved bleach-catalysing effect on coloured stains on hard surfaces. A dishwashing composition that includes these complexes in catalytic amounts as well as a peroxygen compound with or without TAED (N,N,Nxe2x80x2,Nxe2x80x2-tetraacetylethylenediamine) will substantially remove tea stains on porcelain at 45xc2x0 C. in the dishwasher. This holds even for the use of hard water, in which the removal of tea stains is known to be more difficult to achieve than in soft water.
The present invention accordingly further provides for the use of metal complexes containing a tripodal ligand of the formula (1) as catalysts for reactions with peroxy compounds in cleaning solutions for hard surfaces, especially for crockery.
The present invention further provides a hard surface cleaner, especially a cleaner for crockery, a crockery cleaner for use in machine cleaning processes, comprising one of the metal complexes described above containing a tripodal ligand of the formula (1) as a bleach catalyst, and a process for cleaning hard surfaces, especially crockery, using such a bleach catalyst.
The inventive metal complexes containing a tripodal ligand of the formula (1) are also very useful for cleaning hard surfaces, especially tiles, particularly for removing mold stains. Such stains frequently occur especially in the joints between the tiles. These joints may be for example in cementitious and/or gypseous material or in polymer, for example silicone.
The invention accordingly further provides for the use of metal complexes containing a tripodal ligand of the formula (1) as catalysts for reactions with peroxygen compounds in cleaning solutions for tiles and inter-tile joints, and the cleaning solutions used for this purpose that Include a metal complex containing a tripodal ligand of the formula (1) and a peroxide with or without further ingredients such as, for example, surfactants.
The inventive metal complexes containing a tripodal ligand of the formula (1) also provide an excellent antibacterial effect when used together with peroxygen compounds. The use of the inventive metal complexes containing a tripodal ligand of the formula (1) for killing bacteria or for protecting against bacterial colonization accordingly constitutes a further part of the subject-matter of the present invention.
The examples hereinbelow illustrate the invention without limiting it. Parts and percentages are by weight, unless otherwise stated. The ligands are advantageously prepared under argon.